Halogenated derivatives of the naphthoquinone-imine series and a process for their manufacture



Patented Jan. 16, 1951 HALOGENATED DERIVATIVES. OF THE NAPHTHOQUINONE-IMINE SERIES AND A PROCESS FOR THEIR MANUFACTURE Valentin Kartaschofi and Ernst Merian, Basel,

Switzerland, assignors to Sandoz Limited, Basel, Switzerland, a Swiss firm No Drawing. Application June 22, 1948, Serial No. 34,553. In Switzerland June 30, 1947 llvClaims. (01. 260-396) The present invention relates to new halogenated derivatives of the naphthoquinone- :mine series and to a process for their manufacpre.

'- It has been found that new halogenated dewherein at. least one of the :rs stands for a halo-.

gen atom, and dye acetate silk and nylon into violet to reddish-blue shades possessing good fastness properties to light and gas fumes. The following table shows the properties i rivatives of the naphthoquinone-imine series some of the new compounds as compared to the may be prepared by subjecting halogenated starting products and known halogenated naphamino-hydroxy 1.4 naphthoquinon iminesthazarine derivatives.

on. NH 011 0 OH NH on ll H H 1 Br- Br Br- Br -Br B1' Br Br NH1O HO 0H0 0a..-. Golol of the so t' nin: v

ethanol... pure greenish blue. red orange dark blue violet.-. reddish blue blue violet. H2SO..-. yellow..-..-...-.--. lilac carrninered carmine red carmineted. i Y absorption bands in: ethanol 030,579 572,530,494-.... 63%, 584 635,583 636,583,542Cl),

The color reaction of the respective diand trichloro compounds, i. e. the 3.7-dichloro 3.6.7-trichl0roand. 3.6-dich1'oro-5.8-

dihydroxy-l :4-naphthoquinone-imines-(l), is sinular.

(1) during or after their formation to a hydrolysis, whereby the amino group becomes replaced by a hydroxy group giving as final products halogenated 5.8-dihydroxy 1.4 naphthoquinoneinclines-(1).

The halogenated amino-hydroxy 1.4 naphthoquinone-imines-(l) used herein as starting materials can be prepared by halogenation of aminohydroxy 1.4 naphthoquinone imines in the presence of glacial acetic acid, nitro-benzene, chlorobenzene or any other suitable solvent or by halogenation of the reduction products of alpha-alpha dinitronaphthalenes during or after the reduction process in the presence of sulphuric acid.

The hydrolysis of the said aminohydroxy compounds canbelcarried out with mineral acids, diluted withwaterfo'r with mixtures of acids like sulphuric acid and glacial acetic acid. The hydrolysis goes generally very rapidly and the dihydroxy compounds are isolated by pouring their solutions into Water in which. they are in-' on r o:

The following examples illustrate how the invention can be carried out in practice, but are by no means limitative. The parts represent parts by weight.

Example 1 A mixture consisting of '75 parts of 1.5-dinitronaphthalene and 21 parts of sulphur powder is introduced into 1500 parts of sulphuric acid monohydrate and after a homogeneous mixture has been obtained, 300 parts of 40% fuming sul-' phuric acid are added thereto. The charge is stirred and cooled down in. such a manner that the temperature does not increase higher than up to 28 C. A' test specimen taken out shows that it is soluble in ethanol with, a violet colour--- ation. To the reaction mixture are then add-f ed, while cooling, 210 parts. of water in such a" manner that the temperature is maintained .at

20 C. After addition of water; 0.1 part of iodineand 120 parts of bromine are added thereto and the whole heated for about 2 hours at C. At

this temperature the'charge is stirred for 10-12 hours, after which time the whole of the'bro f mine has been taken up. The reaction mixture is then poured into a mixture of. 5000 parts of; ice and 1000 parts of water, filtered and-- washed until free from acid. In this manner 117 parts of a) dark coloured product are ob-- tained which contains about 48.5% of bromine; and 3.6% of N. This product is soluble in eoncentrated sulphuric acid with a sherry-red col ouration that becomes blue-violet on addition;

of paraformaldehyde. It consists merely of dibromo 5.8 dihydroxy 1.4 naphthoquinoneimine(l).

Example 2 f A mixture consisting of 10 parts of 1.5-dinitronaphthalene and 2.8 parts ofsulphur powder is introduced into 200 parts of Sulphuric acid monohydrate and treated at 20 C. with 40 parts of 40% fuming sulphuric acid. When a test specimen taken out shows that the product is soluble in water, 84 parts of water are added to the reaction mixture in such a manner that the temperature does not exceed 25 C. To the reaction mixture are added some iodine and 16 parts of bromine and the whole is heated at 80-85"v C.

After about 3 hours the bromine has completely been taken up. The reaction mixture is poured into a mixture of ice'an'd water, thepre'ci'pitated' product filtered, washed and dried. "In this manner about 18 parts of a dark coloured compound which is soluble in concentrated sulphuric acid with a sherry-red colouration that turns to blue-violet after addition of some paraformald'ehyde is obtained. The new compound is difficultly soluble in ethanol with a blue-violet colouration.

Ercample 3 10"parts of an isomorphously crystallised mixture of 1.5- and l.8-dinitronaphthalenes and 2.8 parts otsulphur powder are introduced into 200 parts'or sulphuric acid monohydrate and treated in the same manner as described in Example 2. About 13 parts of a dark coloured product is obtained which is soluble in concentrated sulphuric acid with a red-brown colouration, but which on addition of some paraformaldehyde becomes violet-brown.

The new product is soluble in hot ethanol with a red-brown colouration.

Example 4 10 parts of 1.8-dinitronaphthalene are reduced and brominated in the manner described in Examplel. 16 parts of a dark coloured product are obtained which is soluble in concentrated sulphuric acid with a red-brown colouration, which becomes violet-black on addition of some paraformaldehyde. In hot ethanol it gives a:

bluish-red solution.

Example 5 V 110 parts of 1.8-dinitronaphthalene are introduced into 1500 parts of"96% sulphuric acid and. heated with good stirring 'at' 125 C. At 'thistemperature there are added by portions within 1 hour 35 parts of iron powder and the reaction mass is stirred for 2-3 hours at 125-130" C. A test specimen taken out dissolves in ethanol with a violet colouration. The charge is thenallowed to cool down to 40 C. and 90 parts of water are added with good cooling." After the addition of water is finished, 1'50parts of bromine are allowed. to run in and thetemperature is increased.

up to '75-90 C. A test specimen taken out dissolves in ethanol with a brown colourationl The stirring and heating is then continued for -12 hours until the reflux of bromine ceases. The. reaction mass is then allowed-to cool down some-2 what and treatedwitha'stream of air inorde'r to blow away the hydrobromic 'acid, then-cooled halogenated quinone-imine-(l) to hydrolysis in dilute su l-- r." dd

, colouration.

Example 6 parts of a technical mixture consisting of diand tri-bromo-5-amino-8-hydroxy-1.4-naphthoquinoneimine-(l) are dissolved in 200 parts of 94% sulphuricacid and stirred during 24 hours underslow addition of 300 parts of glacial ace-.

tic acid. The solution which, at the beginning, was yellow in color becomes green during this treatment, a precipitation of blue needles taking place. The precipitated product is filtered and isolated. It is a tribromo-5.8-dihydroXy-1.4 naphthoquinone-imine-(l). 1

The filtered sulphuric acid solution is then poured into ice and water, whereby a blue precipitate is obtained. It is filtered, washed free from acid and dried. The product thus obtained is dibromo-dd-dihydroxy-l.l-naphthoquinoneimine(l) What we claim is:

l. A process for the manufacture of a halogenated 5.8-dihydroxy-l.4-naphthoquinone-imine- (l) which comprises the step of subjecting a halogenated 5 amino 8 hydroxy 1.4 naphthoquinone-imine-(l) to hydrolysis in an acid medium.

2. A process for the manufacture of a halogenated 5.8-dihydroxy-1.4-naphthoquinone-imine- (1) which comprises the step of subjecting a 5-amino-8hydroxy-1.4-naphthophuric acid.

3. A process for the manufacture of a dihalogenated 5.8 dihydroxy 1.4 naphthoquinoneimine(l) which comprises the step of subjecting a dihalogenated 5-amino-8-hydroxy-L4- naphthoquinone-imine-(l) to lute sulphuric acid.

4. A process for the manufacture of 3.7-dichloro 5.8 dihydroxy 1.4 naphthoquinoneimine(l) comprising the step of subjecting 3.7-

dichloro 5 amino 8 hydroxy 1.4 naphthoquinone-imine(1) to hydrolysis in dilute sulphuric acid. v H

A process for the manufacture of 3 .7 -'dibromo 5.8 dihydroxy- 1.4 naphthoquinone-y imine(l) comprising the step of subjecting 3.7-.

dibromo 5 amino 8 hydroxy 1.4 naphthoquinone-imine-(l) to hydrolysis in dilute.sul.-

phuric acid.

'6; A process for the manuiacturefof 3 .B -'di 1 bromo..-. 5.8 ,dihydroxy l.4 naphthoquinone imine(l) comprising the step of subjecting 3;6 dibromo 5 amino 8 hydroxy 1.4"'-naphthoquinone-imine-(l) to hydrolysis in dilute sulphuric acid.

'7. The halogenated 5:8-dihydroxy-L4-naphthoquinone-imines-(l), selected from the class consisting of the chlorinated: and brominated 5.8 dihydroxy 1.4 'ri'aphthoquinone imines- (1).

hydrolysis in di- 5 8. The dihalogenated 5.8-dihydroxy-lA-naph- 9. The 3,7-dich1or0-5.8-dihydroxy-L4-naphthoquinone-imine- (1) thoquinone-imines-(l) of the formula 0H NH 10. The 3.7dibr0mo-5.8-dihydr0xy-1.-naphll thoquinone-imine 1) 11. The 3.6-dibromo-5.8-dihydroxy-1.4-naphthoquinone-imine- (1) hal VALENTIN KARTASCHOFF.

ERNST MERIAN.

H No references cited.

wherein hal stands for a member of the group 10 consisting of C1 and Br.

hal 

1. A PROCESS FOR THE MANUFACTURE OF A HALOGENATED 5.8-DIHYDROXY-1.4-NAPHTHOQUINONE-IMINE(1) WHICH COMPRISES THE STEP OF SUBJECTING A HALOGENATED 5 - AMINO - 8 - HYDROXY - 1.4 - NAPHTHOQUINONE-IMINE-(1) TO HYDROLYSIS IN AN ACID MEDIUM. 